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SYNONYMS: none
SAMPLING MEASUREMENT
FLOW RATE: 0.5 to 1.5 L/min EXTRACTION: 10 mL 1.75 m M NaHCO 3/2.0 mM Na 2CO 3
FIELD BLANKS: 2 to 10 field blanks per set CONDUCTIVITY SETTING: 10 S full scale
APPLICABILITY: The working range is 0.2 to 8 ppm (0.5 to 20 mg/m 3) for a 100-L air sample. The method is applicable to STEL
samples. SO 2 is collected on the back (treated) filter. Sulfuric acid, sulfate salts, and sulfite salts are collected on the front f ilter
and may be quantitated as total particulate sulfate.
INTERFERENCES: Sulfur trioxide gas, if present in dry atmospheres, may give a positive interference for SO 2.
OTHER METHODS: This revises P&CAM 268 [3]. P&CAM 146 [4], P&CAM 163 [5], and S308 [6] use 0.3 N H 2O 2 for sampling,
followed by titration with NaOH or barium perchlorate. P&CAM 160 [7] uses tetrachloromercurate solution and visible
spectrophotometry. P&CAM 204 [8] uses a solid sorbent (molecular sieve 5A), thermal desorption, and mass spectrometry.
REAGENTS: EQUIPMENT:
1. Water, deionized, filtered, specific 1. Sampler: two 37-mm diameter cassette filter
conductance 10 S/cm. holders (connected in series by a M-M Luer
2. Fixative solution. Dissolve 25 g Na 2CO 3 in adapter, e.g., Millipore XX1102503, or a short
deionized water. Add 20 mL glycerol and piece of plastic tubing) containing:
dilute with deionized water to 1 L. a. (Front cassette) cellulose ester membrane
3. Eluent: 1.75 m M NaHCO 3/2.0 mM Na 2CO 3. filter, 0.8-m pore size, supported by a
Dissolve 0.588 g NaHCO 3 and backup pad.
0.848 g Na 2CO 3 in 4 L filtered b. (Back cassette) cellulose filter (Whatman
deionized water. 40 or equivalent) which has been
4. Calibration stock solutions, saturated with fixative solution and dried
1 mg/mL (as the anion). Prepare 20 to 30 min at 100 C, supported by a
in duplicate. porous plastic support pad.
a. Sulfite: dissolve 0.1575 g 2. Personal sampling pump, 0.5 to 1.5 L/min,
Na 2SO 3 in water. Add 2 mL glycerol. with flexible connecting tubing.
Dilute to 100 mL. Prepare fresh daily. 3. Vials, glass, 20-mL, screw-cap, such as
b. Sulfate: dissolve 0.1479 g scintillation vials.**
Na 2SO 4 in deionized water. Dilute to 4. Ion chromatograph, HPIC-AS4A anion
100 mL. Stable several weeks. separator and HPIC-AG4A guard, anion
micromembrane suppressor, conductivity
detector, and strip chart recorder. (Optional:
* See SPECIAL PRECAUTIONS. integrator.)
5. Syringes, 10-mL, polyethylene, with luer tip.**
6. Filters, in-line, luer-tip holder with membrane
filter, 13- or 25-mm, 0.45-m pore size.
7. Micropipets, 50- to 1000-L, with disposable
tips.**
8. Volumetric flasks, 50- and 100-mL.**
9. Pipet, 10-mL.**
10. Polyethylene bottles, 250-mL.**
SAMPLING:
SAMPLE PREPARATION:
5. Put the two filters from the sampler into separate, clean vials. Discard the backup pads. Add 10.0
mL eluent to each vial and let stand, with occasional vigorous shaking, for 30 min.
NOTE: The SO 2 collected on the treated (back) filter is present as sulfite, which oxidizes in air
slowly (over several weeks) to sulfate. The contributions of sulfite and sulfate found on the
back filter must be summed, with appropriate stoichiometric factors applied, to give the SO 2
concentration (step 11).
6. Pour each sample into a syringe fitted with an in-line filter.
MEASUREMENT:
8. Set ion chromatograph to conditions given on page 6004-1, according to manufacturer's instructions.
9. Inject sample aliquot. For manual operation, inject 2 mL of sample from syringe to ensure complete
rinse of sample loop.
NOTE: All samples, eluents, and water flowing through the ion chromatograph must be filtered to
avoid plugging system valves or columns.
10. Measure peak heights of sulfite and sulfate peaks.
NOTE: If peak height exceeds linear calibration range, dilute with eluent, reanalyze, and apply the
appropriate dilution factor in calculations.
CALCULATIONS:
11. Determine the mass, g, of sulfate equivalent found on the front (W f) and back (W b) filters and in the
corresponding average media blanks (B f and B b).
NOTE: The sulfate equivalent is the sum of the sulfate peak, g, and 1.200 times the sulfite peak,
g, on the chromatogram (1.200 = MW SO 24-/MW SO 23-): g sulfate equivalent = g sulfate +
1.200 g sulfite.
12. Calculate the concentration, C SO2 , of sulfur dioxide, applying the factor 0.667 (MW SO 2/MW SO 24-):
13. Calculate the concentration, C SO4 , of particulate sulfate (including sulfuric acid) in the air volume
sampled, V (L):
EVALUATION OF METHOD:
The sampler was adapted from that of Pate, et al. [9]. In experiments in which SO 2 was generated by
permeation tube and collected in impingers containing H 2O 2, untreated 0.8-m cellulose ester membrane
filters were shown to allow complete passage of SO 2 [10]. In subsequent sampling of an atmosphere
containing ca. 10 ppm SO 2 at 1 L/min for 30 min, two treated filters were placed in series following a
cellulose ester membrane filter. Recoveries were: 0.667 mg SO 2 from the first treated filter, 0.02 mg
SO 2 from the second treated filter, and less than 0.003 mg SO 2 in the backup impinger containing 0.3 N
H2O 2 [11]. Cellulose ester filters spiked with 0.2 mg H 2SO 4 gave the following recoveries: 83.5% using
H2O extraction, 98.5% using hot H 2O extraction, and 82.5% using 0.01 M HCl for extraction.
A study on filter impregnating solutions compared NaHCO 3 and KOH. The chromatograms of samples
from the KOH-treated filters had noticeably flattened and broadened peak shapes as well as retention
times reduced by approximately 10% when compared to the chromatograms of H 2SO 4 spiked on filters
impregnated with NaHCO 3[1].
REFERENCES: